Studies with dithizone: Part XXI. The Relationship between pH12 and Molar Solubility

The effect of changes of ionic strength on the partition of an analytically important weak acid between a variety of aqueous and immiscible organic phases has been studied with respect to new measurements on dithizone (3-mercapto-1,5-diphenylformazan) and di(p-tolyl)thiocarbazone. A linear relationship has been deduced between the pH at which 50% extraction takes place and S_r,o (the solubility of the reactant in the organic phase), and confirmed by measurements of pH_{$\text{1}\text{2}$}, and S_r,o for a large number of organic solvents. The solubilities of the reagents in water, S_r, are also reported. The form of the relationship between pH and log D, and between pH_{$\text{1}\text{2}$} and log S_r,o is the same whether a solution of dithizone consists of a single species or a mixture of thiol and thione forms in tautomeric equilibrium.     

On describing the steady absorption of brownian particles by a restricted random walk

This paper is concerned with idealizing brownian motion as a random walk, using the diffusion equation, and finding the boundary condition at an absorbing surface - all with an eye towards chemical kinetics. Three models of random walk (due to Smoluchowski, Fermi, and Lorentz) are considered, and it is concluded that the lorentzian model is the most appropriate.     

On the long-lived transient absorption observed in nanosecond laser photolysis studies of two polymethine cyanine dyes

It is shown that the long-lived transient absorption which is observed when solutions of cryptocyanine and DDI (1, 1′-diethyl-2, 2′-dicarbocyanine iodide) in methanol and other alcohols are exposed to nanosecond ruby laser pulses arises from a photoproduct whose formation requires consecutive absorption of two photons.     

Performance comparison of an 241Am-Be neutron source-based PGNAA setup with the KFUPM PGNAA setup

Monte Carlo calculations have been carried out to compare the performance of an ²⁴¹Am-Be neutron source-based prompt gamma neutron activation analysis (PGNAA) setup with that of the 2.8 MeV neutron-based PGNAA setup at King Fahd University of Petroleum and Minerals (KFUPM) to analyze Portland cement samples. This work is a part of a wide Monte Carlo studies being conducted at KFUPM in search of a more efficient neutron source for its 2.8 MeV neutrons, from the D(d,n) reaction, based PGNAA facility. In this study an ²⁴¹Am-Be neutron source-based PGNAA setup was simulated. For comparison, the diameter of a cylindrical external moderator of the ²⁴¹Am-Be neutron source, based PGNAA setup, was assumed to be similar to that used in the KFUPM PGNAA setup. The results of this study revealed that although the optimum geometry of the ²⁴¹Am-Be neutron source-based setup is similar to that of the KFUPM PGNAA facility, the performance of the ²⁴¹Am-Be neutron source-based setup is slightly poorer than that of the 2.8 MeV neutron-based setup. This revised version was published online in July 2006 with corrections to the Cover Date.     

The synthesis and ligand properties of the dihydro-bis-(1-indazolyl)borate anion

Summary Potassium dihydro-bis-(1-indazolyl)borate, synthesized from potassium borohydride and indazole, has been used as a reagent to yield complexes with copper(II), nickel(II), cobalt(II), manganese(II) and iron(III) ions. From i.r. spectral studies the ligand is uninegative and bidentate and coordination occurs through the nitrogen atom at position 2 of the indazole ring system in all cases. With the sole exception of the copper(II) complex, the nitrogen atom at position 1 is also involved in forming a bridge with an adjacent metal ion. On the basis of electronic spectral studies and magnetic susceptibility measurements a distorted square planar structure involving chlorine bridges has been proposed for the copper complex. An octahedral geometry with ligand bridges for all complexes is tentatively proposed and it appears that all are polymers.     

Spectral and Mechanistic Investigation of Oxidation of Rizatriptan by Silver Third Periodate Complex in Aqueous Alkaline Medium

The oxidation of Rizatriptan by diperiodatoargentate(III) has been studied by spectrophotometry at neutral pH. The kinetics of the reaction of Rizatriptan has been shown to principle of non-complementary oxidation steps. The initial step involves the deprotonated of the diperiodatoargentate(III) with the alkali; this rearranges during the displacement of a ligand to give free periodate and takes up another ligand monoperiodateargentate(III), combines with a substrate to endow with an intermediate complex which decomposes within a slow step to provide the final product in the following step with a first-order rate constant. The main product was identified by spot test, Fourier- transform infrared spectroscopy, Nuclear magnetic resonance and Liquid chromatography-mass spectrometry spectrum. A conceivable mechanism including pre equilibrium of adducts development between the complex and reductant was planned from the kinetics study. The rate conditions got from system can clarify all exploratory phenomena, and the activation parameters alongside rate constants of the rate determining step were ascertained.     

Epimorphisms, dominions and seminormal identities II

We associate two natural numbers with a seminormal identity depending on the first and the last occurrences of two two-letter subwords of the left hand side which are not subwords of its right hand side. Using these natural numbers, we find some classes of heterotypical identities where both sides contain repeated variables that are preserved under epis in conjunction with a seminormal identity.